KR101050001B1 - Curable composition, sealing agent for liquid crystal display elements, and liquid crystal display element - Google Patents

Abstract

The present invention provides a curable composition that can cope with narrow liquid softening, which reduces contamination to liquid crystals, and has sufficient curability even in a portion shadowed by wiring or the like, and also obtains sufficient adhesiveness not only for a glass substrate but also for a liquid crystal alignment film. to provide.

This invention is curable composition containing the following components (A)-(D); It relates to a liquid crystal sealing agent and a liquid crystal display element comprising the same.

(A) Compound having ethylenically unsaturated group

(B) Partial (meth) acrylic polyfunctional epoxy compound obtained by adding (meth) acrylic acid to a part of epoxy group of the polyfunctional epoxy compound which has three or more epoxy groups in 1 molecule

(C) epoxy curing agent

(D) radical photopolymerization initiator having an oxime ester structure

Curable composition, the liquid crystal sealing agent, the liquid crystal display element, the compound which has an ethylenically unsaturated group, the partial (meth) acrylated polyfunctional epoxy compound, the epoxy hardening | curing agent, the radical photopolymerization initiator which has an oxime ester structure

Description

Curable composition, sealing agent for liquid crystal display elements, and liquid crystal display element {CURABLE COMPOSITION, SEALING MATERIAL FOR LIQUID CRYSTAL DISPLAY DEVICE, AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a radiation curable composition. More specifically, it is related with the radiation curable composition useful as a sealing agent for liquid crystal display elements, and a liquid crystal display element using the same.

Liquid crystal display elements, such as a liquid crystal display cell, are formed by enclosing a liquid crystal between two transparent substrates with electrodes which faced at predetermined intervals. Conventionally, when manufacturing a liquid crystal display cell, first, the pattern which formed the liquid crystal injection hole in the outer periphery of the range which encloses a liquid crystal is formed on one side of two transparent substrates with electrodes by screen printing using a thermosetting sealing agent. . Subsequently, another transparent substrate is opposed to each other with a spacer in between, and the two substrates are bonded to each other and heated to cure the sealant. Next, after inject | pouring a liquid crystal from a liquid crystal injection hole, the liquid crystal injection hole was sealed with the sealing agent. Such a method is generally called a liquid crystal injection method.

The liquid crystal injection system has problems such as a large number of processes, low manufacturing efficiency, misalignment of the substrate due to thermal deformation, fluctuation in intervals, and insufficient adhesion between the liquid crystal sealant and the substrate.

As a means of solving the problem of a liquid crystal injection system, the method called a liquid crystal dropping system is devised now, and the optical thermosetting combined method is mainstream in hardening of a liquid crystal sealing agent. Such a liquid crystal dropping system first forms a rectangular frame which becomes the outer periphery of the range which encloses a liquid crystal with a liquid crystal sealing agent by screen printing on one of two transparent substrates with an electrode. At this time, the liquid crystal injection hole is not formed. Subsequently, in the state of a liquid-crystal sealing agent uncured, a liquid crystal is apply | coated dropwise to the whole surface in this edge, and the other transparent substrate is overlapped and crimped immediately, and an ultraviolet-ray is irradiated to the liquid-crystal sealant part and temporarily hardened. Then, it heats at the time of liquid crystal annealing, and hardens a liquid crystal sealing agent to manufacture a liquid crystal cell.

The liquid crystal dropping method can manufacture a liquid crystal cell efficiently with few processes, and is suitable also for manufacture of a large panel. Moreover, since temporary hardening by ultraviolet-ray is performed, the position shift of the board | substrate by heat deformation is also prevented, and the adhesiveness of a liquid crystal sealing agent and a board | substrate also improves.

However, in the liquid crystal dropping system, since there is a step in which the liquid crystal sealant in the uncured state and the liquid crystal come into contact with each other, a defect occurs in which the components of the liquid crystal sealant are dissolved in the liquid crystal and contaminate the liquid crystal, thereby lowering the specific resistance of the liquid crystal. There is a problem (Patent Document 1).

The curable composition which mix | blended various components is proposed (for example, following patent documents 2-7) for the purpose of reducing the contamination with respect to the liquid crystal by the component of an uncured liquid crystal sealing agent, improvement of sclerosis | hardenability, etc.

However, in recent years, the liquid softening of the liquid crystal display element is requested | required, and by liquid narrowing softening, the liquid crystal sealing agent overlaps with a black matrix and wiring in many cases. In this part, since the ultraviolet-ray is not irradiated to the liquid-crystal sealant, the uncured part remained in the liquid-crystal sealant, and when this contacted with a liquid crystal, the liquid-crystal sealant component eluted and the liquid crystal was polluted.

[Patent Document 1] Japanese Patent Application Laid-Open No. 2001-133794

[Patent Document 2] Japanese Patent Application Laid-Open No. 2004-37937

[Patent Document 3] Japanese Unexamined Patent Publication No. 2003-28004

[Patent Document 4] Japanese Patent Application Laid-Open No. 2005-263987

[Patent Document 5] Japanese Patent Application Laid-Open No. 2005-60651

[Patent Document 6] Japanese Patent Laid-Open No. 2006-30481

[Patent Document 7] Japanese Unexamined Patent Publication No. 2006-58466

As narrowing softening progresses further, the case where a liquid crystal sealing agent overlaps not only the edge of a glass substrate but the edge of a liquid crystal aligning film arises, and the adhesiveness with respect to a liquid crystal aligning film is also calculated | required.

This invention is made | formed in view of the above-mentioned problem, Furthermore, it reduces pollutability to a liquid crystal, has sufficient sclerosis | hardenability also in the part shadowed by wiring etc., and also sufficient adhesiveness is obtained not only a glass substrate but a liquid crystal aligning film. It is an object to provide a curable composition that can cope with narrowing solution softening.

In order to achieve the above object, the present inventors earnestly study, and have an epoxy group and a (meth) acryloyl group in 1 molecule of a liquid under (meth) acrylate monomer, normal temperature, and normal pressure, and also epoxy group and (meth) acryl By using a highly sensitive photo radical initiator having an oxime ester structure for the compound having a total number of royl groups and an epoxy curing agent of 3 or more, it is excellent in workability, low in contamination to liquid crystals, and also good in shadows due to wiring and the like. It discovered that the curable composition which shows sufficient adhesiveness with respect to not only curable and a glass substrate but a liquid crystal aligning film was obtained, and completed this invention.

That is, this invention provides the following curable composition, the liquid crystal sealing agent containing this, and the liquid crystal display element using the same.

1. Curable composition containing following component (A)-(D).

(A) Compound having ethylenically unsaturated group

(B) A compound which has an epoxy group and a (meth) acryloyl group in 1 molecule, and the total number of an epoxy group and a (meth) acryloyl group is three or more

(C) epoxy curing agent

(D) radical photopolymerization initiator having an oxime ester structure

2. The curable composition according to the above 1, wherein the component (B) is a compound obtained by reacting (meth) acrylic acid with a part of an epoxy group of a polyfunctional epoxy compound having three or more epoxy groups in one molecule.

3. The ratio of 2 to 3 in the range of 100: 20 to 100: 80 (molar ratio) of one epoxy group and (meth) acrylic acid of the polyfunctional epoxy compound having three or more epoxy groups in one molecule. Curable composition which is a compound obtained by mixing and reacting as much as possible.

4. Curable composition as described in any one of said 1-3 whose said component (B) is liquid at normal temperature and normal pressure.

5. Curable composition as described in any one of said 1-4 whose epoxy equivalent of the said component (B) exists in the range of 50-2000 on average.

6. The curable composition according to any one of 1 to 5, wherein the radical photopolymerization initiator having the (D) oxime ester structure is represented by the following general formula (d-1).

[Formula d-1]

(Wherein R ¹ represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 10 carbon atoms, R ² represents a hydrogen atom, a phenyl group or an alkyl group having 1 to 10 carbon atoms, and R ³ represents a substituted or unsubstituted carba) Or a Ph-S-Ph-CO- group (Ph represents an aromatic group which may have a substituent)

7. Curable composition as described in any one of said 1-6 whose compound which has said (A) ethylenically unsaturated group is a compound which has 1 or more (meth) acryloyl group.

8. Curable composition as described in any one of said 1-7 which further contains (E) radical photopolymerization initiator which has a structure represented by following General formula (E-1).

[Formula e-1]

[Wherein, R ²⁴ and R ²⁵ each independently represent an alkyl group having 1 to 4 carbon atoms, R ²⁶ represents a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and R ²⁷ represents a hydrogen atom or a methyl group]

9. Curable composition as described in said 8 whose weight ratio of the said component (D) and a component (E) exists in the range of (D) :( E) = 35: 65-65: 35.

10. The curable composition according to any one of 1 to 9, further containing (F) inorganic fine particles.

11. The curable composition according to any one of 1 to 10, further comprising (G) a silane coupling agent.

12. The sealing agent for liquid crystal display elements containing the curable composition in any one of said 1-11.

13. The liquid crystal display element manufactured using the sealing agent for liquid crystal display elements of said 12.

According to the present invention, it is possible to provide a curable composition which is low in contamination with liquid crystals and has good curability even in a portion which is shadowed by wiring or the like and exhibits sufficient adhesiveness not only for the glass substrate but also for the liquid crystal alignment film.

According to this invention, the liquid crystal sealing agent which is especially useful when manufacturing a liquid crystal display element by the liquid crystal dropping method can be provided.

According to the present invention, it is possible to provide a liquid crystal display device excellent in long-term stability by reducing the contamination of the liquid crystal by the uncured liquid crystal sealant.

I. Curable Compositions

Curable composition (henceforth a composition of this invention) of this invention is obtained including the following components (A)-(H). Among the following components, (A) to (D) are essential components, and (E) to (H) are optional components blended as necessary.

(A) Compound having ethylenically unsaturated group

(B) A compound which has an epoxy group and a (meth) acryloyl group in 1 molecule, and the total number of an epoxy group and a (meth) acryloyl group is three or more.

(C) epoxy curing agent

(D) radical photopolymerization initiator having an oxime ester structure

(E) radical photopolymerization initiator having a structure represented by formula (E-1)

(F) inorganic fine particles

(G) silane coupling agent

(H) additive

The curable composition of this invention uses not only a glass substrate but an organic polymer by using the compound which has an epoxy group and a (meth) acryloyl group in 1 molecule (B), and the sum total of an epoxy group and a (meth) acryloyl group is three or more. Sufficient adhesiveness can also be expressed also about the liquid crystal aligning film containing the.

The curable composition of the present invention uses a highly sensitive (D) radical photopolymerization initiator (the radical photopolymerization initiator having an oxime ester structure) to provide a weak ultraviolet scattered light at a shielding site where ultraviolet rays are not directly irradiated by a wiring or a black matrix. Crosslinking reaction of a (meth) acryloyl group advances and can provide high liquid-crystal contamination resistance. Here, "high sensitivity" means that the absorption coefficient of ultraviolet rays is large and even radical light can be generated.

1. Hereinafter, each component is demonstrated.

(A) Compound having ethylenically unsaturated group

The compound which has an ethylenically unsaturated group expresses effects, such as strength improvement, low linear expansion coefficient, and positional stability improvement, as a component to radically polymerize. Although it does not specifically limit as ethylenically unsaturated group, For example, a (meth) acryloyl group, an ethylene group, etc. are mentioned, It is preferable that it is a (meth) acryloyl group.

As a compound which has a (meth) acryloyl group, 2-hydroxyethyl acrylate, 2-hydroxypropyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate, 2-hydroxybutyl ( Meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, isooctyl (meth) acrylate, lauryl (meth) acrylate, stearyl (meth) acrylate, isobornyl ( (Meth) acrylate, cyclohexyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, methoxyethylene glycol (meth) acrylate, 2-ethoxyethyl (meth) acrylate, tetrahydrofurfuryl ( Meth) acrylate, benzyl (meth) acrylate, ethyl carbitol (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, phenoxy polyethylene glycol (meth) acrylate, Methoxypoly Styrene glycol (meth) acrylate, 2,2,2, -trifluoroethyl (meth) acrylate, 2,2,3,3, -tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H, Octafluoropentyl (meth) acrylate, imide (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate, propyl (meth) acrylate, n -Butyl (meth) acrylate, cyclohexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-octyl (meth) acrylate, isononyl (meth) acrylate, isomyristyl (meth) acryl Rate, 2-butoxyethyl (meth) acrylate, 2-phenoxyethyl (meth) acrylate, bicyclopentenyl (meth) acrylate, isodecyl (meth) acrylate, diethylaminoethyl (meth) acrylic Rate, dimethylaminoethyl (meth) acrylate, 2- (meth) acryloyloxyethyl succinic acid, 2- (meth) arc Liloyloxyethylhexahydrophthalic acid, 2- (meth) acryloyloxyethyl 2-hydroxypropylphthalate, glycidyl (meth) acrylate, 2- (meth) acryloyloxyethyl phosphate, 1,4- Butanedioldi (meth) acrylate, 1,3-butanedioldi (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, 1,9-nonanedioldi (meth) acrylate, 1,10- Decanediol di (meth) acrylate, 2-n-butyl-2-ethyl-1,3-propanedioldi (meth) acrylate, dipropylene glycol di (meth) acrylate, tripropylene glycol di (meth) acrylic Elate, polypropylene glycol (meth) acrylate, ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, tetraethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate, propylene Oxide addition bisphenol A di (meth) acrylate, ethylene jade Dide addition bisphenol A di (meth) acrylate, ethylene oxide addition bisphenol F di (meth) acrylate, dimethyloldicyclopentadienyldi (meth) acrylate, 1,3-butylene glycol di (meth) acrylate, neo Pentyl glycol di (meth) acrylate, ethylene oxide modified isocyanuric acid di (meth) acrylate, 2-hydroxy-3- (meth) acryloyloxypropyl (meth) acrylate, carbonatedioldi ( Meth) acrylate, polyetherdioldi (meth) acrylate, polyesterdioldi (meth) acrylate, polycaprolactonedioldi (meth) acrylate, polybutadienedioldi (meth) acrylate, pentaerythritol tree (Meth) acrylate, trimethylol propane tri (meth) acrylate, propylene oxide addition trimethylol propane tri (meth) acrylate, ethylene oxide addition trimethylol Ropantri (meth) acrylate, caprolactone modified trimethylolpropanetri (meth) acrylate, ethylene oxide addition isocyanuric acid tri (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol Hexa (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, pentaerythritol tetra (meth) acrylate, glycerin tri (meth) acrylate, propylene oxide addition glycerin tri (meth) acrylate, tris (Meth) acryloyloxyethyl phosphate etc. are mentioned.

Examples of the (meth) acrylate compound preferably used as the component (A) in the present invention include a (meth) acrylate having a urethane group, a (meth) acrylate having a hydroxyl group, and a (meth) acrylate having a bisphenol skeleton and an epoxy group. (Meth) acrylate which has is preferable.

The (meth) acrylate which has a urethane group can also be obtained by making the compound which has a (meth) acryloyl group and an isocyanate group react with the compound which has a hydroxyl group. As a specific example, ethylene oxide modified isocyanuric-acid di (meth) acrylate etc. are mentioned, for example. As a commercial item of the (meth) acrylate which has a urethane group, U-6HA and U-15HA (made by Shin-Nakamura Chemical Co., Ltd.) etc. are mentioned, for example.

As a specific example of the (meth) acrylate which has a hydroxyl group, ethylene oxide addition bisphenol A di (meth) acrylate, pentaerythritol tetra (meth) acrylate, etc. are mentioned, for example. As a commercial item of the (meth) acrylate which has a hydroxyl group, EB3700 (made by Daicel Cytec Co., Ltd.) etc. is mentioned, for example.

As a commercial item of the compound which has a (meth) acryloyl group which has a bisphenol skeleton and an epoxy group, Uvac1561 (made by Daicel Cytec Co., Ltd.) etc. is mentioned, for example.

The compounding quantity of the component (A) in the composition of this invention is 0.1-90 weight%, Preferably 1-80 weight%, More preferably, 5-70 weight%, when the total amount of a composition is 100 weight%. to be. When the compounding quantity of component (A) is out of the said 0.1-90 weight% range, when irradiated with ultraviolet-ray, a suitable hardness may not be obtained and position shift by heat may become easy to generate | occur | produce.

(B) A compound which has an epoxy group and a (meth) acryloyl group in 1 molecule, and the total number of an epoxy group and a (meth) acryloyl group is three or more.

A compound having an epoxy group and a (meth) acryloyl group in one molecule of the component (B) and having a total number of epoxy groups and (meth) acryloyl groups of three or more (hereinafter referred to as component (B)) is 3 in one molecule. As a compound obtained by adding (meth) acrylic acid to a part of the epoxy group of the polyfunctional epoxy compound which has more than 2 epoxy groups, it is preferable that it is a liquid at normal temperature and normal pressure. Here, "a liquid at normal temperature and normal pressure" means that the viscosity under normal temperature and normal pressure is 5,000 Pa * s or less, Preferably it is 1,000 Pa * s or less, More preferably, it is 100 Pa * s or less. Here, "normal temperature" means 25 degreeC specifically, and "normal pressure" means atmospheric pressure (0.1 mPa) specifically. The said viscosity is the measured value using the Brookfield viscometer in 25 degreeC. When a component (B) is a liquid at normal temperature and normal pressure, the liquid crystal sealing agent using this as a raw material becomes low viscosity, and it is excellent in workability.

By mix | blending a component (B), the effect that contamination with a liquid crystal is suppressed and adhesive strength with respect to an oriented film improves is acquired.

A component (B) is obtained by adding (meth) acrylic acid to a part of epoxy groups of the polyfunctional epoxy compound which has three or more epoxy groups in 1 molecule, and does not have a (meth) acryloyl group. As a specific example of the epoxy group of the polyfunctional epoxy compound which has three or more epoxy groups in one molecule, and does not have a (meth) acryloyl group, For example, sorbitol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol Polyglycidyl ether, diglycerol polyglycidyl ether, trimethylol propane polyglycidyl ether and the like. As for the epoxy compound used as the raw material of the component (B) used by this invention, sorbitol polyglycidyl ether, trimethylol propane polyglycidyl ether, etc. are preferable at the point that resin liquid crystal contamination is low, and a viscosity is low. Do. Since these epoxy compounds are low viscosity, the liquid crystal sealing agent containing the component (B) which used this as a raw material becomes low viscosity, and is excellent in workability.

It is preferable that it is in the range of 50-2,000, and, as for the epoxy equivalent of the epoxy compound used as the raw material of a component (B), it is more preferable to exist in the range of 60-1000. Here, "epoxy equivalent" means the molecular weight of the epoxy compound per epoxy group. If the epoxy equivalent is less than 50, there is a risk of adversely affecting the stain resistance to the liquid crystal, if larger than 2000, there is a fear that sufficient curing strength may not be obtained.

As an example of the commercial item of the epoxy compound used as a raw material of a component (B), for example, GT401 (the tetrafunctional epoxy compound by Daicel Chemical Industries, Ltd.), EX-321 (the trifunctional by Nagase Chemtex) Epoxy compound), EX-411 (4-functional epoxy compound manufactured by Nagase Chemtex Co., Ltd.), EX-614B (4-functional epoxy compound manufactured by Nagase Chemtex Co., Ltd.), SR-SEP (Sakamoto Yakuching High School Co., Ltd.) ) Polyfunctional epoxy compound).

The epoxy compound used as the raw material of component (B) may be used individually by 1 type, and may be used in combination of 2 or more type.

In order to partially (meth) acrylate the epoxy compound of a raw material, you may mix a polymerization inhibitor, a catalyst, and (meth) acrylic acid with an epoxy compound, and you may stir at 50 degreeC-100 degreeC for about 3 to 20 hours. Examples of the catalyst to be reacted include tetrabutylammonium bromide, triphenylphosphine, triethylamine and the like. It is preferable to use tetrabutylammonium bromide in terms of condensation reaction and side reaction.

The ratio of the polyfunctional epoxy compound which becomes a raw material of a component (B), and (meth) acrylic acid makes one epoxy group and (meth) acrylic acid of a polyfunctional epoxy compound into the range of 100: 20-100: 80 (molar ratio). It is preferable that it is preferable to carry out in the range of 100: 40-100: 60 (molar ratio). When the amount of (meth) acrylic acid to react is outside the said range, contamination of a liquid crystal may be concerned, and there exists a possibility that sufficient adhesive force with respect to a board | substrate may not be obtained.

In addition, the ratio of the (meth) acryl group in the component (B) which introduce | transduced the (meth) acryl group as mentioned above is 1 / n-(when the number of the epoxy groups of the polyfunctional epoxy compound of a raw material is n). It is necessary to be in the range of n-1) / n.

Although the polyfunctional epoxy compound which is not the partial (meth) acrylated material which is a raw material of component (B) is excellent in adhesiveness (adhesiveness) to both a glass substrate and an oriented film, when it mixes in large quantities, there exists a possibility that liquid-crystal contamination may worsen. Was found.

On the other hand, by mix | blending the (B) partial (meth) acrylic polyfunctional epoxy compound, sufficient adhesiveness can be expressed not only in a glass substrate but also in a liquid crystal aligning film, and also the balance of adhesiveness (adhesiveness) and liquid-crystal contamination property with respect to an oriented film Can catch.

The compounding quantity of the component (B) in the composition of this invention is 0.1-90 weight%, Preferably it is 1-80 weight%, More preferably, 5-60 weight% when making the total amount of a composition 100 weight% to be. When the blending amount of the component (B) is out of the range of 0.1 to 90% by weight, sufficient adhesive strength may not be obtained or, when irradiated with ultraviolet rays, an appropriate hardness may not be obtained and position shift due to heat is likely to occur. There is this.

(C) epoxy curing agent

An epoxy curing agent is mix | blended in order to bridge | crosslink the compound containing an epoxy group, and to express the effect of adhesiveness and hardness. As an epoxy hardening | curing agent, an acidic compound, an acid generator, a basic compound, or a base generator is mentioned. Moreover, as an epoxy hardening | curing agent, it is preferable to use the "latent type epoxy hardening | curing agent" in which hardening | curing agent itself performs a crosslinking reaction with an epoxy group and is introduce | transduced in the crosslinked polymer.

As the latent type epoxy curing agent, known ones can be used, and organic acid dihydrazide compounds, imidazoles and derivatives thereof, dicyandiamide, aromatic amines and the like are preferable in view of providing a one-component compound having good viscosity stability. . These may be used alone or in combination.

Among these, as a latent type epoxy hardening | curing agent, it is more preferable that it is an amine latent type hardening | curing agent, and the softening point temperature by its melting | fusing point or ring-ball method (based on JIS K2207) is 100 degreeC or more.

When the amine latent type curing agent is used, the active hydrogen of the amine causes a thermonuclear addition reaction to the (meth) acryloyl group of another component having a (meth) acryloyl group in the composition of the present invention. Curability of the composition is improved.

That is, since an amine latent type hardening | curing agent shows a thermal reaction characteristic with respect to both the compound which has an ethylenically unsaturated group of component (A), and / or the epoxy compound of component (B), it functions as a compatibilizing component of both components, The panel reliability, such as the display characteristic of a liquid crystal display panel, adhesive reliability, becomes favorable, and is preferable.

In addition, although the upper limit of the softening point temperature by melting | fusing point or the round ball method is not specifically limited, Usually, it is 250 degrees C or less.

As an amine latent type hardening | curing agent and the latent type epoxy hardening | curing agent whose melting point or softening point temperature by a ring method is 100 degreeC or more, For example, dicyandiamide, such as dicyandiamide (melting point 209 degreeC); Organic acid dihydrazides such as adipic dihydrazide (melting point 181 ° C.) and 1,3-bis (hydradinocarboethyl) -5-isopropylhydantoin (melting point 120 ° C.); 2,4-diamino-6- [2'-ethylimidazolyl- (1 ')]-ethyltriazine (melting point 215 ° C to 225 ° C), 2-phenylimidazole (melting point 137 to 147 ° C), Imidazole derivatives such as 2-phenyl-4-methylimidazole (melting point 174 to 184 ° C), 2-phenyl-4-methyl-5-hydroxymethylimidazole (melting point 191 to 195 ° C), and the like. have.

In addition, it is preferable to use the latent type epoxy hardening | curing agent used for this invention by what performed the high purity treatment by the washing method, the recrystallization method, etc.

As an example of the commercial item of the said amine type latent hardening | curing agent, amicure VDH, VDH-J, UDH, UDH-J (made by Ajinomoto Fine Techno Co., Ltd.) etc. are mentioned, for example.

A latent type epoxy curing agent may be used individually by 1 type, and may be used in combination of 2 or more type.

The compounding quantity of the component (C) in the composition of this invention is 0.1-60 weight%, Preferably 1-50 weight%, More preferably, 3-30 weight% when making the total amount of a composition 100 weight% to be. When the compounding quantity of component (C) is less than 0.1 weight%, there exists a possibility that sclerosis | hardenability with an epoxy may be inadequate, sufficient hardness and adhesiveness may not be obtained, and the possibility of liquid-crystal contamination may become high. Moreover, when more than 60 weight%, there exists a possibility that the possibility that an excess hardening agent which does not react with an epoxy may contaminate a liquid crystal may become high.

(D) radical photopolymerization initiator having an oxime ester structure

The radical photopolymerization initiator used in the present invention is a compound having an oxime ester structure. The compound having an oxime ester structure is highly sensitive, and the composition of the present invention can be cured by reflected light, scattered light, or diffracted light even at a site where shadows such as wiring or a black matrix are not directly irradiated.

It is preferable that the compound which has an oxime ester structure is a compound represented by following General formula (d-1).

<Formula d-1>

In formula (d-1), R ¹ is preferably a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms.

R ² is preferably a hydrogen atom, a phenyl group, or an alkyl group having 1 to 10 carbon atoms.

R ³ is preferably a monovalent organic group including a substituted or unsubstituted carbazole group, or a Ph-S-Ph-CO- group (Ph represents an aromatic group which may have a substituent).

Moreover, O-acyl oxime type compound is mentioned as a compound which has a preferable oxime ester structure as a component (D). As an O-acyl oxime type compound, the carbazole type O-acyl oxime type polymerization initiator is preferable. For example, 1- [9-ethyl-6-benzoylcarbazol-3-yl] -nonane-1,2-nonane-2-oxime-O-benzoate, 1- [9-ethyl-6-benzoylcar Bazol-3-yl] -nonane-1,2-nonane-2-oxime-O-acetate, 1- [9-ethyl-6-benzoylcarbazol-3-yl] -pentane-1,2-pentane-2 Oxime-O-acetate, 1- [9-ethyl-6-benzoylcarbazol-3-yl] -octane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methylbenzoyl ) Carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl] -ethan-1-one Oxime-O-acetate, 1- [9-ethyl-6- (1,3,5-trimethylbenzoyl) carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9- Butyl-6- (2-ethylbenzoyl) carbazol-3-yl] -ethane-1-one oxime-O-benzoate, 1- [9-ethyl-6- (2-methyl-4-tetrahydropyranylme Methoxybenzoyl) carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- (2-methyl-4-tetrahydrofuranylmethoxybenzoyl) carbazole-3- Work〕- Ethane-1-one oxime-O-acetate, 1- [9-ethyl-6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] carbazole-3 -Yl] -1- (O-acetyl oxime) etc. are mentioned.

Among these O-acyl oxime compounds, in particular, 1- [9-ethyl-6- (2-methylbenzoyl) carbazol-3-yl] -ethane-1-one oxime-O-acetate, 1- [9-ethyl- Preference is given to 6- [2-methyl-4- (2,2-dimethyl-1,3-dioxolanyl) methoxybenzoyl] carbazol-3-yl] -1- (O-acetyloxime).

As an example of the commercial item of the compound which has an oxime ester structure, CGI242, OXE01 (made by Ciba Specialty Caicals Co., Ltd.), N-1919 (made by Adeka Co., Ltd.), etc. are mentioned, for example.

The radical photopolymerization initiator of component (D) may be used individually by 1 type, and may be used in combination of 2 or more type. Moreover, it can also use combining a suitable sensitizer and a chain transfer agent. The thing which provided the crosslinkable group to the radical radical initiator itself can also be used.

The compounding quantity of the component (D) in the composition of this invention is 0.01-20 weight%, Preferably it is 0.1-15 weight%, More preferably, 0.2-10 weight weight when making the total amount of a composition 100 weight%. %to be. When the compounding quantity of component (D) is less than 0.01 weight%, there exists a possibility that the crosslinkability of an acryl group may become inadequate, sufficient hardness and dimensional stability may not be obtained, and the possibility of liquid-crystal contamination may become high. Moreover, when more than 20 weight%, it does not harden to the inside (lower part), and there exists a possibility that liquid crystal contamination possibility may become high similarly.

(E) radical photopolymerization initiator having a structure represented by formula (E-1)

The radical photopolymerization initiator of the component (E) is a compound having a structure represented by the following formula (E-1).

<Formula e-1>

In the formula, R ²⁴ and R ²⁵ each independently represent an alkyl group having 1 to 4 carbon atoms, R ²⁶ represents a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and R ²⁷ represents a hydrogen atom or a methyl group.

The photopolymerization initiator of component (E) may have a structure in which a plurality of chemical formulas e-1 are connected, and the molecular weight in that case is preferably in the range of 350 to 10,000.

By using together with the radical photopolymerization initiator which has the oxime ester structure of the said component (D), the contamination with respect to a liquid crystal can be reduced more effectively. As for the compounding ratio (weight ratio) of the initiator of component (D) and the initiator of component (E), it is preferable that component (D): component (E) exists in the range of 35: 65-65: 35, and it is 50:50. Particularly preferred. When there is little component (D), dark part sclerosis | hardenability falls, On the contrary, when too much, contamination resistance with respect to a liquid crystal may fall. If it is in the said range, the curable composition excellent in all the performance of adhesiveness, the stain resistance to liquid crystal, and dark part curability will be obtained.

As a specific example of the radical photopolymerization initiator of the component (E) used by this invention, the oligo (2-hydroxy- 2-methyl- 1- [4- (1-methylvinyl) phenyl] prop represented by following formula (e-2) Panon can be mentioned.

[Formula e-2]

(Wherein k represents a number from 2 to 50)

As a commercial item of the radical photopolymerization initiator of the component (E) used by this invention, Escure KIP150 and 150P (above, Sartomer make) are mentioned, for example.

The compounding quantity of the component (E) in the composition of this invention is 0.01-20 weight%, Preferably 0.1-15 weight%, More preferably, 0.2-10 weight%, when the total amount of a composition is 100 weight%. to be. When the compounding quantity of component (E) is less than 0.01 weight%, there exists a possibility that liquid-crystal contamination may deteriorate. Moreover, when more than 20 weight%, there exists a possibility that liquid-crystal contamination and adhesive strength may fall. In addition, the compounding quantity of component (E) should be determined in consideration of the ratio with the compounding quantity of component (D).

(F) inorganic fine particles

By mix | blending an inorganic fine particle, since it becomes a high glass transition temperature and a low linear expansion coefficient, and the effect of dimensional stability improvement can be expressed (improvement, improvement), it is used preferably.

Examples of the inorganic fine particles include particles mainly composed of silica, alumina, zirconium oxide, magnesium oxide, calcium carbonate, magnesium carbonate, barium sulfate, talc, montmorillonite, and the like. Particles mainly containing silica and alumina are preferable.

The shape of an inorganic fine particle may be any of spherical shape, rod shape, plate shape, fiber shape, and indefinite shape, and these may be solid shape, hollow shape, and porous shape.

The number average particle diameter of the inorganic fine particles is usually in the range of 0.001 to 10 µm, preferably 0.01 to 5 µm. When it exceeds 10 micrometers, there exists a possibility that the space formation of the glass substrate bonding at the time of liquid crystal cell preparation may be difficult. Here, the number average particle diameter of an inorganic fine particle is measured by the laser beam diffraction method.

The inorganic fine particles may be added and mixed with a powdery thing directly to other components, or may be added to and mixed with another component with a solvent dispersion liquid to distill off the solvent.

As an example of the commercial item of an inorganic fine particle, For example, admafine SO-E1, SO-E2, SO-E3, SO-E4, SO-E5 (made by Admatex Co., Ltd.), SS01, SS03, SS15, SS35 (The Osaka Kasei Co., Ltd. product) etc. are mentioned.

An inorganic fine particle may be used individually by 1 type, and may be used in combination of 2 or more type.

The inorganic fine particles may be surface treated with a silane coupling agent or the like. By performing such surface treatment, compatibility with other components can be improved and the dispersibility and mechanical strength in a composition can be improved.

As a commercial item of the surface-treated silica particle, admapa SE3200-SEJ (made by Admatex Co., Ltd .; epoxy modified silica microparticles | fine-particles), etc. are mentioned, for example.

The compounding quantity of the component (F) in the composition of this invention is 1-50 weight%, Preferably it is 5-40 weight%, More preferably, it is 10-30 weight% when making the total amount of a composition 100 weight%. to be. When the compounding quantity of component (F) is less than 1 weight%, there exists a possibility that dimensional stability may deteriorate. Moreover, when more than 50 weight%, there exists a possibility that the space formation of the glass substrate bonding at the time of liquid crystal cell preparation may not become good.

(G) silane coupling agent

By mix | blending a silane coupling agent, since the effect of the durability improvement of adhesive strength can be expressed (improved, improved), it is used preferably.

As a silane coupling agent, what has an epoxy group and what has a (meth) acryloyl group are preferable.

A silane coupling agent may be used individually by 1 type, and may be used in combination of 2 or more type.

As an example of the silane coupling agent which has an epoxy group, (gamma)-glycidoxy propyl trimethoxysilane etc. are mentioned, for example. As an example of the commercial item of these silane coupling agents, SH6040 (made by Toray Dow Corning Co., Ltd.), KBM-403 (made by Shin-Etsu Silicone Co., Ltd.), etc. are mentioned, for example.

As an example of the silane coupling agent which has a (meth) acryloyl group, (gamma)-methacryloxypropyl trimethoxysilane etc. are mentioned, for example. As an example of the commercial item of these silane coupling agents, SZ6030 (made by Toray Dow Corning Co., Ltd.), KBM-503, KBM-5103 (made by Shin-Etsu Silicone Co., Ltd.), etc. are mentioned, for example.

The compounding quantity of the component (G) in the composition of this invention is 0.001-15 weight%, Preferably it is 0.01-10 weight%, More preferably, 0.05-5 weight% when making the total amount of a composition 100 weight% to be. When the compounding quantity of component (G) is less than 0.001 weight%, there exists a possibility that sufficient adhesive durability may not be obtained. Moreover, when more than 15 weight%, there exists a possibility that liquid crystal contamination possibility may become high.

(H) other additives

The other additive can be mix | blended with the composition of this invention in the range which does not impair the effect of this invention. As such an additive, radical radical initiators, sensitizers, chain transfer agents, antifoamers, ion trapping agents, absorbers, organic fine particles, leveling agents, spacers, organic solvents, etc. other than component (D) and (E) are mentioned, for example. .

2. Manufacturing Method of Curable Composition

In the composition of the present invention, the components (A) to (D) and, if necessary, the components (E) to (H) are placed in a container, sufficiently mixed using a stirrer such as a planetary stirrer, and then degassed under vacuum. It can manufacture by performing.

3. Curing method and curing conditions of the curable composition

The composition of the present invention can be cured either by ultraviolet irradiation or by heating.

When using the composition of this invention as a liquid crystal sealing agent, and using the liquid crystal dropping method, it temporarily hardens by ultraviolet irradiation, and then it hardens by heating further.

Although the wavelength of the light used in order to harden the composition of this invention is not specifically limited, 350-700 nm is preferable in consideration of damage to an orientation film or a liquid crystal. The irradiation dose is preferably 500 to 10000 mJ / cm 2, more preferably 1000 to 3000 mJ / cm 2.

Although it does not specifically limit as temperature of thermosetting, Preferably, curing temperature is 70 degreeC or more and less than 200 degreeC, More preferably, it is 100 degreeC or more and less than 150 degreeC. Moreover, as hardening time, Preferably they are 20 minutes or more and less than 3 hours, More preferably, they are 30 minutes or more and less than 2 hours.

II. Liquid crystal sealant

A liquid crystal sealing agent is used in order to adhere | attach two glass substrates of a liquid crystal display element, to protect an inside, and to prevent outflow of a liquid crystal.

The liquid crystal sealing agent of this invention contains the curable composition of the said invention, It is characterized by the above-mentioned. Therefore, the liquid crystal sealing agent of this invention is equipped with liquid-crystal contamination resistance, dark part curability, tensile adhesive strength with respect to a glass substrate, and a liquid crystal aligning film, etc., and is useful for manufacture of the liquid crystal display element (liquid crystal display cell) by a liquid crystal dropping method. .

Although the viscosity of the liquid crystal sealing agent of this invention is not specifically limited, From a viewpoint of distribution and shape preservation, Preferably it is 10-1000 Pa.s, More preferably, it is 100-500 Pa.s.

III. Liquid crystal display device

The liquid crystal display element of this invention is manufactured using the liquid crystal sealing agent of the said invention, It is characterized by the above-mentioned. Therefore, according to this invention, the liquid crystal display element which is excellent in liquid-crystal contamination resistance and tensile adhesive strength, and excellent in long-term stability and reliability is obtained.

The structure of the liquid crystal display element of this invention is demonstrated, referring the schematic diagram of one Embodiment of the liquid crystal display element of this invention shown in FIG.

As shown in FIG. 1, the liquid crystal display device 1 includes a spacer 18 between the transparent electrode 14, the alignment film 12, and the two glass substrates 10 provided with the color filter 16. It has a structure which hold | maintains the liquid crystal 22 with a liquid crystal sealing agent across this.

The liquid crystal sealant 20 bonds two glass substrates 10 together, and seals and holds the liquid crystal 22 in a space surrounded by the glass substrate 10 and the liquid crystal sealant 20. Further, for narrowing the softening, the width of the edges of the glass substrate 10 tends to be small, and the sealing portion by the liquid crystal sealant is often also hypothesized in the alignment film 12, and not only the glass substrate but also the liquid crystal alignment film. Adhesiveness is required.

As can be seen from FIG. 1, since the liquid crystal sealant 20 is in direct contact with the liquid crystal 22, if a component in the uncured liquid crystal sealant 20 is dissolved in the liquid crystal 22, the liquid crystal The specific resistance of (22) is reduced, resulting in the loss of long-term stability and reliability of the liquid crystal display element 1.

Since the liquid crystal sealant of this invention uses the liquid crystal sealant of the said invention, since the uncured liquid crystal sealant component is prevented from melt | dissolving in a liquid crystal, it is excellent in long-term stability and reliability.

It is preferable that the liquid crystal display element of this invention is manufactured by the liquid crystal dropping method. 2, the outline | summary of the manufacturing process of the liquid crystal display element by a liquid crystal dropping system is demonstrated.

On one glass substrate, the frame of the liquid crystal sealing agent which surrounds the range which encloses a liquid crystal is formed using a dispenser. The line width and film thickness of a liquid crystal sealing agent are respectively 0.1-5 mm and about 0.1-20 micrometers normally, and it is preferable that they are 0.5-3 mm and 1-10 micrometers, respectively. As a dispenser of the liquid crystal sealing agent used at this time, SHOTminiSL (made by Musashi Engineering Co., Ltd.) etc. are mentioned.

After hardening a liquid crystal in the frame of a liquid crystal sealing agent, and removing a bubble etc., without hardening a liquid crystal sealing agent, the other glass substrate is bonded together, two glass substrates are crimped | bonded, and a liquid crystal is sealed.

Next, light is irradiated and the liquid crystal sealing agent is temporarily hardened. It is preferable to use the thing of wavelength 200-700 nm for the light used at this time, and when it considers the damage to an oriented film or a liquid crystal, it is more preferable to use the thing of wavelength 350-700 nm. It is preferable to use a high pressure mercury lamp, a metal halide lamp, an LED, etc. as a light source.

Thereafter, the substrate is heated at 70 to 200 ° C, preferably 90 to 150 ° C for 10 minutes to 5 hours, preferably 30 minutes to 2 hours to perform liquid crystal annealing, and at the same time, the liquid crystal sealant is cured. Obtain a liquid crystal display element.

Hereinafter, although an Example and a comparative example are given and this invention is demonstrated further more concretely, this invention is not limited at all by these Examples.

Preparation Example 1

Synthesis of hydroxyl-containing urethane acrylate ((A) component glycerin-AOI)

To a solution containing 75.4 parts of 2-isocyanate ethyl acrylate (Karens AOI manufactured by Showa Denko Co., Ltd.) and 0.1 part of dibutyltin dilaurate in a container with a stirrer, glycerin (Sakamoto Yakuching High School ( 24.6 parts of purified glycerin) manufactured by dropwise addition were added dropwise under conditions of 10 ° C and 1 hour, and then stirred under conditions of 60 ° C and 4 hours to obtain a reaction solution.

When the amount of residual isocyanate of the product in this reaction liquid was measured by FT-IR, it was confirmed that reaction was performed almost quantitatively as 0.1 mass% or less. Moreover, it was confirmed that a molecule | numerator contains a urethane bond and acryloyl group (polymerizable unsaturated group).

As a result, 100 parts of glycerin-AOI were obtained.

Production Example 2

Synthesis of partially acrylated polyfunctional epoxy monomer (EX-411 acrylic acid adduct)

In a reaction vessel equipped with a thermometer, a stirrer, and an air blowing device, 100 parts of Denacol EX-411 (4-functional epoxy monomer manufactured by Nagase Chemtex Co., Ltd .; epoxy equivalent 233), 21.1 parts of acrylic acid, and tetrabutylammonium bromide 0.5 The part was added, heated to 70 ° C while blowing air into the reaction vessel, and the mixture was stirred at that temperature for about 12 hours. It confirmed that acrylic acid reacted, it cooled, and the monomer containing the polymerizable unsaturated group in which half in the epoxy groups in 1 molecule of epoxy monomers was acryl-added was obtained. It was confirmed by NMR and FT-IR that the acrylic group and the epoxy group were introduced 1: 1 in the monomer.

Production Example 3

Synthesis of partially acrylated polyfunctional epoxy monomer (EX-614B acrylic acid adduct)

In a reaction vessel equipped with a thermometer, a stirrer, and an air blowing device, 100 parts of Denacol EX-614B (manufactured by Nagase Chemtex Co., Ltd .; epoxy equivalent 171), 21.1 parts of acrylic acid, and tetrabutylammonium bromide 0.5 The part was added, heated to 70 ° C while blowing air into the reaction vessel, and the mixture was stirred at that temperature for about 12 hours. It confirmed that acrylic acid reacted, it cooled, and the monomer containing the polymerizable unsaturated group in which half in the epoxy groups in 1 molecule of epoxy monomers was acryl-added was obtained. It was confirmed by NMR and FT-IR that the acrylic group and the epoxy group were introduced 1: 1 in the monomer.

Preparation Example 4

Synthesis of partially acrylated polyfunctional epoxy monomer (EX-610UP acrylic acid adduct)

In a reaction vessel equipped with a thermometer, a stirrer, and an air blowing device, 100 parts of Denacol EX-610-UP (manufactured by Nagase Chemtex Co., Ltd .; 4-functional epoxy monomer; epoxy equivalent weight 228), 15.8 parts acrylic acid, and tetrabutylammonium 0.5 part of bromide was thrown in, and it heated up to 70 degreeC, blowing air into a reaction vessel, and stirred at that temperature for about 12 hours. It confirmed that acrylic acid reacted, it cooled, and the monomer containing the polymerizable unsaturated group in which half in the epoxy groups in 1 molecule of epoxy monomers was acryl-added was obtained. It was confirmed by NMR and FT-IR that the acrylic group and the epoxy group were introduced 1: 1 in the monomer.

Preparation Example 5

Synthesis of partially acrylated polyfunctional epoxy monomer (EX-321 acrylic acid adduct)

In a reaction vessel equipped with a thermometer, a stirrer, and an air blowing device, 100 parts of Denacol EX-321 (trifunctional epoxy monomer manufactured by Nagase Chemtex Co., Ltd .; epoxy equivalent 139), 25.9 parts of acrylic acid, and tetrabutylammonium bromide 0.5 The part was added, heated to 70 ° C while blowing air into the reaction vessel, and the mixture was stirred at that temperature for about 12 hours. It confirmed that acrylic acid reacted, it cooled, and the monomer containing the polymerizable unsaturated group in which half in the epoxy groups in 1 molecule of epoxy monomers was acryl-added was obtained. It was confirmed by NMR and FT-IR that the acrylic group and the epoxy group were introduced 1: 1 in the monomer.

Example 1

The component shown in Example 1 of the following Table 1 was weighed in the container, and it fully mixed using the planetary stirrer (Awato Renta Co., Ltd. make). Thereafter, degassing was performed under vacuum to prepare a curable composition.

Examples 2-11 and Comparative Examples 1-7

Each curable composition was produced like Example 1 except having set it as the composition shown in following Tables 1 and 2.

<Characteristic Evaluation of Hardened Materials>

The following characteristics at the time of hardening the curable composition obtained by the said Example and comparative example were evaluated. The results obtained are shown in Tables 1 and 2.

1. Glass tensile adhesive strength

A curable composition is taken in the center part of a slide glass, another slide glass is overlapped so that it may cross, and it may be crimped | bonded and it will be set to uniform thickness. After irradiating this with ultraviolet (500 mW / cm <2>, 3000 mJ / cm <2>), it was left to stand at 120 degreeC for 1 hour, and it was set as the sample for tensile adhesive strength measurement. The adhesive strength (N / cm <2>) of this sample was measured with the tensile tester. If it is 400 N / cm <2> or more, tensile adhesive strength is favorable.

2. Alignment film tensile adhesive strength

What disperse | distributed 1 weight part of spacer particle with respect to 100 weight part of curable compositions is taken in the center part of the orientation film part slide glass, and another alignment film part slide glass is superimposed so that it may cross, and it may be crimped | bonded and it will be set to uniform thickness. After irradiating this with ultraviolet (500 mW / cm <2>, 3000 mJ / cm <2>), it was left to stand at 120 degreeC for 1 hour, and it was set as the sample for tensile adhesive strength measurement. The adhesive strength (N / cm <2>) of this sample was measured with the tensile tester. If it is 400 N / cm <2> or more, tensile adhesive strength is favorable.

The oriented film part glass substrate used at this time was dipped into the optimizer AL60101 (made by JSR Corporation) on the slide glass, and was apply | coated uniformly on a board | substrate by spin-coating, and it prebaked 90 degreeC for 1 minute with a hotplate. It can obtain by carrying out post-baking 200 degreeC in oven for 1 hour.

3. Liquid Crystal Phase Transition Temperature Change

After putting the curable composition 0.025g in the sample bottle (10 mm inside diameter), 0.075g of liquid crystals (MLC-6608 by Merck) was put. After irradiating an ultraviolet-ray (3000 mJ / cm <2>) from the bottom face of this sample bottle, it was left to stand at 120 degreeC for 1 hour. After cooling to 25 degreeC, the supernatant liquid crystal was taken out and DSC measurement was performed (temperature rising rate 2 degree-C / min). The change amount was calculated | required from the difference of the measured phase transition temperature and the phase transition temperature of the unprocessed liquid crystal (blank), and it evaluated according to the following evaluation criteria.

○: The difference (change amount) is less than 0.5 ° C for the blank.

(Triangle | delta): The difference (change amount) with respect to a blank is 0.5 degreeC or more and less than 1.0 degreeC

X: The difference (amount of change) is 1.0 degreeC or more with respect to a blank.

The commercial item of Table 1 and 2 shows the following.

EB3700: Bisphenol A-containing epoxy acrylate made by Daicel Cytec Co., Ltd.

Glycerin-AOI (synthesized in Preparation Example 1)

EX-411: 4-functional epoxy compound manufactured by Nagase Chemtex Co., Ltd., epoxy equivalent 233

EX-614B: 4-functional epoxy compound manufactured by Nagase Chemtex Co., Ltd., epoxy equivalent 171

EX-610UP: Nagase Chemtex Co., Ltd. product tetrafunctional epoxy compound, epoxy equivalent 228

EX-321: trifunctional epoxy compound manufactured by Nagase Chemtex Co., Ltd., epoxy equivalent 139

EX-411 acrylic acid adduct: synthesized in Preparation Example 2

EX-614B: Synthesis in Preparation Example 3

EX-610UP: Synthesis in Preparation Example 4

EX-321 acrylic acid adduct: synthesized in Preparation Example 5

Amicure UDH-J: latent type epoxy curing agent manufactured by Ajinomoto Fine Techno Co., Ltd.

N-1919: radical photopolymerization initiator manufactured by Adeka Co., Ltd.

KIP150: Photo radical polymerization initiator produced by Sartomer Co., Ltd.

Admafine SE3200-SEJ: epoxy modified silica fine particles manufactured by ADMATEX Co., Ltd.

SH6040: A silane coupling agent manufactured by Toray Dow Corning Corporation; γ-glycidoxypropyltrimethoxysilane

Although the comparative examples 1-7 which mix | blended the polyfunctional epoxy compound which was not partially acrylated from the result of Table 1 and 2 are excellent in both a glass tensile adhesive strength and an oriented film tensile adhesive strength, when a compounding quantity increases, liquid-crystal contamination property deteriorates. Able to know. On the other hand, in Examples 1 to 11 in which the partially acrylated polyfunctional epoxy compound is blended, even if the amount is large, there is less liquid crystal contamination, and a balanced composition satisfying the properties of liquid crystal contamination, glass tensile adhesive strength and alignment film tensile adhesive strength. It can be seen that.

The liquid crystal sealant of the present invention is sufficiently cured even in a portion where the sealant portion and the ultraviolet ray overlapped with the wiring or the black matrix are not directly irradiated by a recent request for narrowing solution softening, so that the adhesion between the glass substrate and the alignment film is sufficient. This high, uncured liquid crystal sealant component can also reduce the possibility of liquid crystal contamination.

According to this invention, the liquid crystal sealing agent useful in the liquid crystal dropping method which can manufacture a liquid crystal display element efficiently with few process water can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is a cross-sectional schematic diagram of the liquid crystal display element of this invention.

2 is a diagram illustrating an outline of a liquid crystal dropping method.

<Explanation of symbols for the main parts of the drawings>

1: liquid crystal display element

10: glass substrate

12: alignment film

14: transparent electrode

16: color filter

18: spacer

20 liquid crystal sealant

22: liquid crystal

Claims (13)

(A) a compound having an ethylenically unsaturated group, (B) A compound which has an epoxy group and a (meth) acryloyl group in 1 molecule, and the total number of an epoxy group and a (meth) acryloyl group is three or more, (C) epoxy curing agent, (D) Curable composition containing the radical photopolymerization initiator which has an oxime ester structure. The curable composition according to claim 1, wherein the component (B) is a compound obtained by reacting (meth) acrylic acid with a part of an epoxy group of a polyfunctional epoxy compound having three or more epoxy groups in one molecule. The compound obtained by mixing and reacting (meth) acrylic acid so that it may become 20 to 80% by molar ratio with respect to the epoxy group of the polyfunctional epoxy compound which has the said 3 or more epoxy groups in 1 molecule, The compound (B) of Claim 2 Phosphorus curable composition. The curable composition according to any one of claims 1 to 3, wherein the component (B) is a liquid at normal temperature and normal pressure. The curable composition according to any one of claims 1 to 3, wherein the epoxy equivalent of the component (B) is in the range of 50 to 2000 on average. The curable composition according to claim 1, wherein the radical radical polymerization initiator having the (D) oxime ester structure is represented by the following general formula (d-1). <Formula d-1>

(In formula, R <^1> represents a hydrogen atom, a phenyl group, a C1-C10 alkyl group, R <^2> represents a hydrogen atom, a phenyl group, a C1-C10 alkyl group, R <^3> is a substituted or unsubstituted carbazole group, Or Ph-S-Ph-CO- group (Ph represents an aromatic group which may have a substituent) The curable composition according to any one of claims 1 to 3, wherein the compound (A) having an ethylenically unsaturated group is a compound having at least one (meth) acryloyl group. (E) Curable composition as described in any one of Claims 1-3 which further contains the radical photopolymerization initiator which has a structure represented by following General formula (E-1). <Formula e-1>

[Wherein, R ²⁴ and R ²⁵ each independently represent an alkyl group having 1 to 4 carbon atoms, R ²⁶ represents a hydroxyl group or an alkyl group having 1 to 4 carbon atoms, and R ²⁷ represents a hydrogen atom or a methyl group] The curable composition of Claim 8 whose weight ratio of the said component (D) and a component (E) exists in the range of (D) :( E) = 35: 65-65: 35. The curable composition according to any one of claims 1 to 3, further comprising (F) inorganic fine particles. The curable composition according to any one of claims 1 to 3, further comprising (G) a silane coupling agent. The sealing agent for liquid crystal display elements containing the curable composition of any one of Claims 1-3. The liquid crystal display element manufactured using the sealing agent for liquid crystal display elements of Claim 12.

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